东平湖CDOM吸收光谱特性及其来源解析

为分析东平湖有色可溶性有机物（CDOM）吸收特性、来源和空间分布的季节变化,分别于2013年8、12月以及2014年3月采集了35个表层水样,分析了各基本水质参数、CDOM吸收系数[a（440）]、比吸收系数[a^*（440）]和相对分子量参数M值的分布规律及CDOM吸收系数与水质参数之间的相关关系.结果表明：东平湖CDOM吸收系数a（440）呈现出枯水期 > 丰水期 > 平水期的规律,空间分布与CDOM比吸收系数[a^*（440）]相似.M值呈现出丰水期 < 平水期 < 枯水期的变化趋势.丰水期CDOM吸收系数与叶绿素a（Chla）具有显著相关关系;丰、平水期两季CDOM吸收系数与DOC存在显著相关关系.丰水期CDOM同时受外源和内源输入的影响,但以内源输入为主,主要来源于浮游植物降解产物;老湖镇湖区外源特征明显.平水期CDOM亦受内源和外源输入的双重影响,但浮游植物的腐烂降解不是CDOM的主要来源;北部湖区以外源输入为主.枯水期CDOM整体表现出较强的自生源特征,但相关分析显示,浮游植物降解并不是CDOM的主要来源,自生源特征可能与挖沙活动导致的悬浮物浓度增高有关;东南湖区因大汶河输入的影响呈现出较强的外源特征.利用东平湖丰、平水期两季CDOM浓度反演DOC浓度具有可行性.     

Organic aerosol molecular composition and gas–particle partitioning coefficients at a Mediterranean site (Corsica)

Molecular speciation of atmospheric organic matter was investigated during a short summer field campaign performed in a citrus fruit field in northern Corsica(June 2011). Aimedat assessing the performance on the field of newly developed analytical protocols, this work focuses on the molecular composition of both gas and particulate phases and provides an insight into partitioning behavior of the semi-volatile oxygenated fraction. Limonene ozonolysis tracers were specifically searched for, according to gas chromatography–mass spectrometry(GC–MS) data previously recorded for smog chamber experiments. A screening of other oxygenated species present in the field atmosphere was also performed. About sixty polar molecules were positively or tentatively identified in gas and/or particle phases. These molecules comprise a wide range of branched and linear, mono and di-carbonyls(C_3–C7),mono and di-carboxylic acids(C_3–C_18), and compounds bearing up to three functionalities.Among these compounds, some can be specifically attributed to limonene oxidation and others can be related to α- or β-pinene oxidation. This provides an original snapshot of the organic matter composition at a Mediterranean site in summer. Furthermore, for compounds identified and quantified in both gaseous and particulate phases, an experimental gas/particle partitioning coefficient was determined. Several volatile products, which are not expected in the particulate phase assuming thermodynamic equilibrium, were nonetheless present in significant concentrations. Hypotheses are proposed to explain these observations, such as the possible aerosol viscosity that could hinder the theoretical equilibrium to be rapidly reached.     

Trace element partitioning in ashes from boilers firing pure wood or mixtures of solid waste with respect to fuel composition,chlorine content and temperature

Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature.Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.     

Acid-catalyzed heterogeneous reaction of 3-methyl-2-buten-1-ol with hydrogen peroxide

Acid-catalyzed heterogeneous oxidation with hydrogen peroxide(H2O2) has been suggested to be a potential pathway for secondary organic aerosol(SOA) formation from isoprene and its oxidation products. However, knowledge of the chemical mechanism and kinetics for this process is still incomplete. 3-Methyl-2-buten-1-ol(MBO321), an aliphatic alcohol structurally similar to isoprene, is emitted by pine forests and widely used in the manufacturing industries. Herein the uptake of MBO321 into H2SO4–H2O2mixed solution was investigated using a flow-tube reactor coupled to a mass spectrometer. The reactive uptake coefficients(γ) were acquired for the first time and were found to increase rapidly with increasing acid concentration. Corresponding aqueous-phase reactions were performed to further study the mechanism of this acid-catalyzed reaction. MBO321 could convert to 2-methyl-3-buten-2-ol(MBO232) and yield isoprene in acidic media. Organic hydroperoxides(ROOHs) were found to be generated through the acid-catalyzed route,which could undergo a rearrangement reaction and result in the formation of acetone and acetaldehyde. Organosulfates, which have been proposed to be SOA tracer compounds in the atmosphere, were also produced during the oxidation process. These results suggest that the heterogeneous acid-catalyzed reaction of MBO321 with H2O2 may contribute to SOA mass under certain atmospheric conditions.     

中小城市空气环境指标的多角度分析研究——以楚雄市为例

文章根据楚雄市空气污染数据,采用统计的方法从不同的角度探求中小城市空气污染指标的变化规律,并求出三种污染物的同时置信区间及它们之间的关联性。结果表明:楚雄市的空气污染主要由SO2造成,室外空气质量能达到一类地区的水平,三种污染物之间两两相关性较弱,但整体相关性较强,同时根据结论提出了相应的建议。     

决策偏好对水环境污染物总量分配的影响

总量分配是制订污染物总量控制方案的基础,在总量分配方法中合理性指数法是由各因素组成的多目标分配方法,是一种新方法、新思路.由于各因素之间对应的权重系数通常采用专家打分方法确定,因此,分析主观性对总量分配结果的影响具有十分重要的意义.论文共选取30名不同领域的人员,并进行分组,分别对权重因子进行打分,分析不同类型的人员权重分布的特点及其对污染物总量分配结果的影响.研究结果表明:不同人员的权重因子对污染物总量分配具有一定的影响,对最后的决策结果产生一定的不确定性.从分配总量结果来看,TN、TP平均值分别为1.64万t·a-1、0.12万t·a-1,标准差分别为0.16万t·a-1、0.014万t·a-1,变差系数分别为0.09、0.12;从分组结果来看,管理人员一致性较好,研究人员一致性较差.总体而言,综合考虑不同领域专家的意见是保持总量分配方案的合理性和一致性的有效途径.     

青岛大气中HNO3、HNO2、NH3及PM2.5中氮组分的浓度特征和气-粒平衡关系

研究PM2.5中NO-3、NO-2、NH+4及其气态前体物HNO3、HNO2、NH3的浓度特征和气-粒平衡关系,对深入认识PM2.5的来源及控制因素具有重要意义.因此,本文利用2012年6—7月在青岛采集的denuder和PM2.5大气样品,分析了其中气态和颗粒态氮组分的浓度.结果发现,青岛大气中HNO3、HNO2和NH3浓度分别为(0.80±0.79)μg·m-3、(0.49±0.59)μg·m-3和(4.71±4.03)μg·m-3,PM2.5中NO-3、NO-2和NH+4的浓度分别为(7.50±9.00)μg·m-3、(0.07±0.02)μg·m-3和(8.23±5.57)μg·m-3.HNO3气体浓度的昼夜变化具有统计意义上的显著差异,白天平均为1.16μg·m-3,高于夜晚的0.44μg·m-3,但其他氮组分无显著昼夜差异.观测期间,青岛大气为富氨环境,PM2.5中NH+4主要以(NH4)2SO4的形式存在,NO-3生成主要受HNO3的限制.利用ISORROPIA II热力学平衡模型探讨了青岛PM2.5中氮组分的控制因子,通过敏感性实验发现,颗粒态NO-3和NH+4分别对总HNO3(TN)和总H2SO4(TS)的变化响应敏感,而对总NH3(TA)的变化响应不敏感,这暗示了减少大气中TN和TS而不是TA对降低青岛PM2.5浓度更有效.     

Characterization of polycyclic aromatic hydrocarbons in urban stormwater runoff flowing into the tidal Anacostia River, Washington, DC, USA

To investigate the sources, fate, and transport dynamics of PAHs (polycyclic aromatic hydrocarbons) in stormwater runoff that is a leading source of pollution in urban watersheds, storm and base flow samples were collected in six branches along the lower Anacostia River. PAHs in storm flow (1510-12,500 ng/L) were significantly enriched in the particle phase, which accounted for 68-97% of the total PAHs. It suggests that reducing particles in stormwater using post-treatment system would decrease PAHs considerably. The solid-water distribution coefficients (KD) of PAHs in the storm flow samples were up to 340 times higher than predicted values. A greater portion of high molecular weight PAHs and their distribution patterns indicate higher contribution of automobile originated pyrogenic PAHs. Total suspended solids in storm flow had a positive relationship with flow rates and exceeded benchmark level for the protection of aquatic biota in some samples.     

Chemical Partitioning to Foliage: The Contribution and Legacy of Davide Calamari

- DOI: http://dx.doi.org/10.1065/espr2006.01.002 Background Davide Calamari and his colleagues were among the first to appreciate that vegetation could play a key role in determining the fate and effects of organic contaminants. They conducted pioneering experiments to investigate the uptake of contaminants by plants from the atmosphere and they sought to model the observed phenomena. In the nearly two decades since there has been a marked increase in understanding of these phenomena as a result of both experimental and modelling studies. - Goal. In this study we briefly review our current understanding of chemical partitioning between foliage and air. A model in both fugacity and concentration format is described, based on that of Tolls and McLachlan (1994), in which the leaf is treated as consisting of two layers, a waxy cuticle with an underlying 'reservoir' layer, the cuticle being surrounded by an air boundary layer and containing stomata that provide direct access from the air to the 'reservoir'. The model quantifies the dynamic penetration of a defined chemical into a defined leaf as a function of time. Main Features The model is applied for illustrative purposes to a hypothetical but typical leaf for a set of illustrative chemicals to demonstrate the effect of changes in physical-chemical properties and leaf characteristics. Discussion The results are compared qualitatively with a variety of field and laboratory studies of foliage uptake and clearance of chemicals. Conclusion It is concluded that the model yields results that are generally consistent with observations. It is suggested that with appropriate parameterisation and validation, the model can contribute to an improved understanding of the process of foliage uptake from the atmosphere and to the development of an improved predictive capability.     

A PARTITIONING PROCEDURE FOR WATER QUALITY MANAGEMENT MODELS1

ABSTRACT: An improved computational procedure for solving water quality management models containing interacting pollutants and control policies is presented. The method is developed with respect to the specific problem of minimizing the costs of basin-wide thermal and organic pollution control to meet water quality standards. It views the problem in partitioned form where a master problem is used to find cooling levels for thermal polluters while subproblems determine optimal organic pollutant reductions for fixed cooling levels. A gradient based search procedure is used to solve the master problem. Computational results for several river systems are presented. Application of the method to other water quality management models is suggested.